Electrical control system



Nov. 26, 1946. JY, A. VAN DEN AKKER ALWZ ELECTRICAL CONTROL SYS TEM Original Filed Sept. 2, 1941 9 Sheets-Shea?l l Zara/0 NOV- 26, 1946 J. A. VAN DEN AKKx-:R

ELECTRICAL CONTROL SYSTEM Original Filed Sept. 2, 1941 9 Sheets-Sheet 2 C21-ats @Moa/wm,

EN@ hg NN@ www NOV- 26, 1945- J. A. VAN DEN AKKER -,2,411,672

ELECTRICAL CONTROL SYSTEM Original Filed Sept. 2, 1941 9 Sheets-Sheet 3 @a/22 726515 /z 05222 gg/5er NOV 2.6, 1946- J. A. VAN DEN AKKER 2,411,572

ELECTRICAL CONTROL SYS TEM Original Filed Sept. 2, 1941 9 Sheets-Shea?l 4 Screen de ?Z 507'.-

NOV- 25, 1945- J. A. VAN DEN AKKER ELECTRICAL CONTROL SYSTEM Original Filed Sept. 2, 1.941 9 Sheets-Sheet 5 NNN Z dem C/Mmfan 04,2 51er NOV- 26, 1946- J. A. VAN DEN AKKER 2,411,672

ELECTRICAL CONTROL S YS TEM Original Filed Sept. 2, 1941 9 Sheets-Shc-zefl 6 NOV 26, 1946- J. A. VAN DEN AKKER gy-LW? ELECTRICAL CONTROL SYSTEM Original Filed Sept. 2, 1941 9 Sheets-Sheet 7 9 Sheets-Sheet 8 NNN L T WQN u J. A. VAN DEN AKKER ELECTRICAL CONTROL SYSTEM Original Filed Sept. 2, 1941 Nova, 26,1946.

Jig/4M, @md @hw Nov. 26, 1946. J. A. VAN DEN AKKER ELECTRICAL CONTROL SYSTEM Original Filed Sept. 2, 1941 9 Sheets-Sheet 9 zde/z an @22 ger Hagar/Z 35 Cm fwgdm atented ov. 26, 194

ELECTRICAL CONTROL SYSTEM Johannes A. Van den Akker, Appleton, Wis., as-

signor to The Institute of Paper Chemistry, a corporation of Wisconsin Original application September 2, 1941, Serial No. 409,174. Divided and this application October 2S, 1943, Serial No. 507,958

9 Claims. 1

My invention relates, generally, to apparatus for measuring and recording concentrations of substances which have the property of absorbing light energy of certain wavelengths, the apparatus being particularly adapted to measure and record small concentrations of such substances. As will hereinafter appear, the disclosed embodiment of the invention includes a new and useful light conversion and selection system, photometer, and electrical circuit, each of which serves as one of the component parts of the concentration recording apparatus, but which are not limited solely to use with this apparatus. This application is a division of my co-pending application, Serial No. 409,174, which was iiled on September 2, 1941, and which is assigned to the assignee of this application. My earlier application matured into Patent No. 2,356,001 on May 30, 1944.

It is a known scientiiic fact that certain substances have the property of strongly absorbing light of certain wavelengths, particularly in the ultraviolet region of the spectrum. Examples of gases and vapors having such a property are ozone, sulphur dioxide, mercury vapor, chlorine, perchloroethylene, phosgene, and a fairly large group of other gases and vapors. Examples of solutes which in solution have the property of absorbing light of certain wavelengths are potassium diohromate, amino disulfonic acids, and sodium benzoate. In general, light energy absorption by these various substances is proportional to, or bears a definite relation to, their concentration.

The present invention, making use of this light absorption principle, provides an inexpensive and practical concentration recorder for accurately measuring and simultaneously recording concentrations of substances having this particular property of appreciable absorption for light radiation of certain wavelengths. Although there is some literature treating in a general way on this phenomenon of light absorption by certain substances, and some progress has been made in developing apparatus for only measuring or indicating the concentrations of such substances depending upon their particular light absorption property, it does not appear that there has been any substantial progress made in developing apparatus for both measuring and recording in a continuous manner the concentrations of such substances depending upon their light absorption properties.

Accordingly, the object of my invention, generally stated, is to provide an inexpensive, practical apparatus for measuring and continuously recording in an accurate manner the concentration of certain gases, vapors, and solutes having the property of absorbing to an appreciable extent light radiation of certain particular wavelengths.

A specific object of this invention is to provide an inexpensive and practical concentration recorder which is particularly adapted to accurately measure and record small concentrations of ozone.

Another object of this invention is the provision of an inexpensive light conversion and selection system which makes possible the use of a commercial light source or lamp which emits light in a plurality of wave bands as a source of light energy in a single one of the emitted bands. This light conversion and selection system is particularly adapted for use as part of my improved concentration recorder but may be put to certain other important applications.

In obtaining maximum sensitivity of response in the apparatus of the present invention, an electrical bridge circuit has been provided which produces large changes in wave form in response to relatively small changes in light flux. This bridge circuit is particularly adapted to control gas-filled electric valves, and although it is particularly adapted for use in connection with concentration recorders embodying my invention, it may be advantageously employed in connection with other applications.

rIhe nature and principles of my invention may be more fully understood from the following detailed description of an ozone concentration recorder which forms one embodiment of the invention. Extended tests have shown that this ozone concentration recorder is commercially practical and will accurately measure and record small concentrations of ozone in a very satisfactory manner.

In the interests of simpliiication, the detailed description of the selected embodiment of the invention will be preceded by a brief discussion of the basic principles of operation thereof taken in connection with suitable diagrammatic drawings.

In the drawings:

Fig. 1 is a diagram of a simple basic system by which the concentration of a substance may be measured depending upon its property of absorbing light radiation of a particular wavelength;

Fig. 2 is a diagram of a system similar to that shown in Fig. 1, but employing the light conversion and selection system of the present invention instead of a monochromatic illuminator;

Fig. 3 is a comprehensive diagrammatic View of a concentration recorder embodying the features of the'present invention;

Fig. 4 is a view taken generally on line 4--4 of Fig. 3;

Fig. 5 is a diagrammatic View of a photometer aperture forming an important part of the present invention;

Fig, 6 is a mathematical diagram by which the principles of construction and design of the photometer of Fig. 5 may be explained;

Figs. 7, 8 and 9 are electrical diagrams or wave form sketches by means of which certain electrical observations important in connection with the electrical bridge circuit of the present invention may be explained;

Fig. 10 is a diagram of a light-sensitive electrical bridge circuit adapted to produce large .changes in wave form in response to small relative changes in illumination of a pair of photo- Vcells and forming an important feature of my present invention;

Fig. 11 is a diagram or sketch showing changes in Wave form produced by the electrical bridge circuit of Fig. 10;

Fig. 12 is a diagram showing an electrical control system by which a reversible motor may be controlled in response to changes in Wave form produced by an electrical bridge circuit embodying the essentials of the bridge circuit of Fig. 10;

Figs. 13a and 13b are horizontal sectional views of a successfully operated and tested ozone concentration recorder instrument made in accordance with the principles of the present invention, Figs. 13sand 13b together forming a complete horizontal section through this apparatus;

Fig. 14a is a vertical sectional view taken on A line Illa-Ida of Fig. 13a;

Fig. 14h is a Vertical sectional View taken on line Ide-Mb of Fig. 13b;

Fig. 15 is an elevational view of a mercury vapor lamp taken on line I5-I 5 of Fig. 13a;

Fig. 16 is a vertical sectional view taken on line Iii-I5 of Fig. 13a;

Fig. 17 is a circuit diagram of the electrical control system for the ozone concentration recorder instrument in Figs. 13a, 13b, 14s and 14h;

and

Fig. 18 is a diagram of a modied form of lightsensitive electrical bridge which has been advantageously substituted for the electrical bridge of the electrical control system shown in Fig. 17. In the electrical bridge of Fig. 18 the photoelectric cells are of the photo-emissive type, whereas in Fig. 17 the photoelectric cells are of the blocking-layer type.

Ozone gas has the ability to strongly absorb ultraviolet light of certain wavelengths. In particular, the absorption by ozone gas of light radiation n the 253.1 mmu line of the mercury spectrum is exceedingly strong, the extinction coeicient being 149 cnr-1, under standard conditions of temperature and pressure. That is, a layer of ozone having a thickness of 1 cm. Will, under standard conditions of temperature and pressure, reduce the intensity of 253.7 mmu radiation to 1/10149. A Lauchli (Z. Physik, 53:92 (1929)), reported extinction coefcients a for ozone gas under standard conditions of normal pressure and temperature, as follows:

Table I Wavelength: 237.8 248.2 253.7 265.2 280.4 296.7 312.5 324.1 mmu a: 1130.5 141. 149. 123. 45.6 6.9 0.96 107cm-1 4 The extinction coefficient a is defined by the equation:

where I0 and I are, respectively, the intensities of incident and transmitted radiation, a is the extinction coefhcient, and h is the thickness of the layer of ozone gas in centimeters. Thus transmittance T of a quartz cell containing ozone gas may be expressed by the equation where p is the mass of ozone per cubicAcentimeter, and a is the absorption coeflicient per unit concentration and per unit thickness of gas. Under standard conditions of temperature and pressure, 13:0.00214 g./cc.; therefore a-- a/p=149/0.00214=69,700 cm2/g. From this, p may be expressed by the equation: (3) p=(1/ah 10210 (l/T) Applying the foregoing data, it will be seen that the system shown in Fig. 1 can be used to measure the concentration of ozone gas. Referring to Fig, 1, a mercury arc, indicated diagrammatically at I0, is used as a source of 253.7 mmu radiation. The radiation of 253.7 mmu wavelength is isolated from radiation of other wavelengths emitted from the arc IS by a quartz monochromatic illuminator, indicated diagrammatically at I I. An absorption cell I2, through which ozone gas may be circulated, is placed in line with the monochromatic illuminator i i so as to receive 253.7 mmu radiation transmitted therethrough. Radiation passing through the cell I2 is received by a photocell I3 adapted to be sensitive to ultraviolet light through the use of fluorescent screen (not shown) which may be prepared, for example, by dipping plain transparent Cellophane in a solution of Uranine B dye. The system is completed by a galvanometer, indicated diagrammatically at HI, having its terminals connected with the terminals of the photocell I3.

In operation, as 253.7 mmu radiation passes through the absorption cell I2 its intensity is reduced to an extent depending upon the concentration of ozone therein. In turn, the photo-current produced by the photocell depends upon the intensity of the 253.7 mmu radiation incident thereon. Accordingly, the amount of deiection of the galvanometer I4 Will depend upon the concentration of the ozone circlulated through the absorption cell I 2.

To calibrate the apparatus, a table of galvanometer deflections with corresponding ozone concentrations may be prepared for the system of Fig. 1 as follows:

As above stated, the mass of ozone per cubic centimeter p is related to the transmittance T in accordance with Equation 3.

p=(1/h) logio (l/T) Now since a and h are constant, and T is Iproportional to the deflection D of the galvanometer when I0 is constant, we have Equation (4) p=k1 logic (l/D) The value of k1 maybe determined -by observing the deflection D1 for a known concentration p1 of ozone, then substituting these known values in Equation 4 and solving for k1. Having determined k1, a calibration table for the system ,may be calculated by substituting diiferent values `for D and solving for corresponding values for p.

Byusing absorption cells of different gas thickness h, ozone concentrations -in different ranges can be measured with good accuracy.

Although the ozone concentration indicating system of Fig. 1 is successful in `operation from a `scientific standpoint, it necessitates the vuse of the monochromatic illuminator II. Accordingly, to eliminate this piece of apparatus, .the system shown in Fig. 2 was provided.

Referring to Fig, 2, a mercury vapor lamp I5 is shown which serves as a source of ultraviolet light for the system. A Westinghouse Sterilamp having an M-shape was found to serve very satisfactorily a-s this mercury vapor lamp I5. Over 88 per `cent of the radiation from the lamp I5 is concentrated in the 253.7 mmu line of the mercury spectrum and the detailed distribution of the energy in the various lines thereof is given in the following table:

A quartz absorption cell I6 through which ozone gas may `be circul-ated is disposed in front of the lamp I5, and a glass plate I1 coated with a 4thin layer or deposit of cadmium borate phosphor is placed in line with the cell IB to receive radiation transmitted therethrough. The cadmium bor-ate phosphor is strongly excited Iby radiation of 253.7 mmu wavelength, is weakly excited by near `ultraviolet light, and receives-no excitation at all from visible light. When excited by ultraviolet ligh-t alone, the cadmium borate phosphor iluoresces in the orange and red part of the spectrum.

According to R. N. Thayer and B. T. Barnes (J. Optical Soc. Am. 29:131 (March, 1939)), the spectral excitation curve of cadmium borate phosphor is negligible for wavelengths -greater than approximately 380 mmu and, in going toward shorter wavelengths, rises very steeply, being very substantial at a wavelength of 253.7 mmu. When the values for relative energy given in Table I are multiplied by the spectral excitation values given by Thayer and Barnes, the excitation due to 253.7 mmu radiation, and excitations vdue to neighboring lines are obtained as given in the following table:

It will be seen from Table III that the relative excitation of the fluorescent-plate I'I due rto 253.7 mmu radiation is 11,300, whereas that due to the neighboring lines inthe ultraviolet has a total of only about 153. Computation shows that the amount of excitation due to radiation emitted from the lamp I5 in the neighboring lines of the mercury spectrum is only 1.4 percent of that due to 253.7 mmu radiation. As can be seen from Luchlis data in Table I above, these neighboring lines are somewhat absorbed by ozone but, assuming they suffered no absorption (this enables computation of maximum error), an idea of the error involved can be obtained by taking a transmittance value T of the ozone in the absorption cell I6 as equal to 0.500. The observed transmittance would then be M[11h00/21+ 153 (5) T* "11,300+153 If this corresponds to a concentration of ozone of 1.00 percent, the observed concentration would be 0.98 percent. This is only an error of 2 percent of the value of the concentration itself. When `the concentration of ozone 0:0.5 percent, T=O.707; the observed T would be 0.711 and Sc=0.008, or about 1.6 percent of the concentration itself. These discrepencies are satisfactorily small and may be compensated for in calibration of the instrument.

Fluorescent radiation from the plate II, which is most strong in the red portion of the spectrum, is filtered through a filter I8 before it reaches a photocell I9. The filter I8 may be a Wratten No. 25 filter which excludes or absorbs all direct radiation of wavelength less than 580 mmu, but freely passes radiation of longer wavelength. Hence, the response of the photocell I9 due to the lines 578.0, 546.1, 435.9 mmu, etc., in the system, will be negligible. The residual response due to the visible spectrum of the mercury arc will be due to the very feeble lines in the red and near infra-red, If not accounted for, this radiation in the red and near infra-red portions of the spectrum would give rise to a concentration error of a smallness comparable with that under 2.0 percent discussed above in connection with Equation 5. Instrument calibration may be relied upon to take care of this small error. Accordingly, the photocell I9 (which may be of the blocking-layer type) will give rise to a photocurrent which is primarily dependent upon and responsive to the intensity of 253.7 mmu radiation.

The deflection of a galvanometer 20 connected in series with the photocell I9 will be proportional to the photocurrent produced thereby. With a uniform amount of 253.7 mmu radiation being supplied to the absorption cell I6 from the mercury vapor lamp I5, the photocurrent will be proportional to the intensity of the 253.7 mmu radiation transmitted through the absorption cell I6, and accordingly will vary inversely with the ozone concentration therein. To calibrate the apparatus, a table of galvanometer deiiections and corresponding values of ozone concentration may be prepared for the system of Fig. 2 according to the method as described above in connection with the system of Fig. 1.

The systems described above in connection with Figs, l and 2 of the drawings serve only to measure or indicate ozone concentrations. Such apparatus, while perhaps suitable for measuring the concentration of ozone in various gas samples from time to time, is inadequate since there are many applications and instances where it is necessary to measure and record the concentrations of ozone and other gases and vapors in a ontinuou's manner. In Figs. 3'and 4 of the drawings, such a system for measuring and recording 'ozone concentrations in a continuous manner is shown. The general arrangement and broad principles of operation of my concentration recorder may be conveniently understood by a brief, general description thereof taken in connection with Figs, 3 and 4, while a detailed description of the various operating parts and elements thereof can be advantageously given below.

Accordingly, referring to Figs. 3 Vand V4 of the drawings, there is shown at 25 a mercury .vapor lamp, which may be in the form of an M-shaped Westinghouse Sterilamp, and which serves as a source of ultraviolet light. Ihe light energy distribution characteristics of the vapor lamp 25 have been described above in connection with the mercury vapor lamp I5 of Fig. 2. A pair of quartz-window absorption cells 26 and 21 are placed to the right of the lamp so as to receive ultraviolet light therefrom. The rays of radiation from the lampy 25 to the cells 26 and 21 are indicated in broken line. The upper absorption cell 26 serves as the active cell through which ozone gas may be circulated, When the concentration of ozone or other gas or vapor in air is being measured it is not necessary to provide the lower absorption cell 21. However, when the concentration of a solute in a solvent is being measured, the clear solvent should be placed in the lower absorption cell 21.

A plate 28 is placed a short distance to the right of the absorption cells 26 and 21, this plate having two rectangular openings or Windows 29 and 30 formed therein. The windows 26 and 36 register with the upper and lower absorption cells 26 and 21, respectively, so that light from the lamp 25passing through the absorption cells 26 and 21 alsov passes through the openings 29 and 36. A photometer member 3l, the construction and design of which is described in detail hereinafter, is shiftably mounted in front of the upper opening 29. The photometer member 3| and the opening 29 together form a variable photometer aperture for measuring light passing through the upper absorption cell 26. An adjustable shutter member 32 is provided in the back of the lower window 33 which serves to adjust the Width thereof.

A pair of the light conversion and selection systems described in connection with the system of Fig. 2 of the drawings are incorporated in the concentration recorder of Fig. 3; that is to say, the system or combination formed by the fluorescent plate I1 and the lter I8 of Fig. 2. In Fig. 3, a cadmium borate phosphor coated plate 33 is positioned to the right of the upper opening 29, while a similar fluorescent plate 34 is positioned to the right of the window 36. The fluorescent plates 33 and 34 may have the same excitation characteristics as the fluorescent plate I1 described in connection with Fig. 2. 'A pair of red filters 35 and 36 are placed to the right and in back of the fluorescent plates 33 and 34 respectively, so as to receive fluorescent light therefrom. The filters 35 and 36 may be of the Wratten No. 25, or A lter type, having the absorption characteristics described in connection with filter I8 of Fig. 2. A pair of photocells 31 and 3B are placed behind the filters 35 and 36, respectively, so as to receive light passing therethrough. A horizontal partition 36 ,serves to separate the upperfset Vof elements from the 'Cil -lower set so as to prevent Ainterference due to light leakage` therebetween.l

When the concentration recorder of Fig. 3 is being used to measure and record ozoneconcentration, the mercury vapor lamp 25 serves as a source of 253.7 mmu radiation. The fluorescent plate 33 and filter 35 forming the upper. set, of light conversion and selection elements, transform the ultraviolet 253.7 mmu radiationinto visible light and isolate thegother neighboring lines of the mercury spectrum, so that the response of the upper photocell 31 is substantially entirely due to the amount of 253.7 mmu radial,tion passing the photometer. The manner, in which this light conversion and isolation is accomplished is described above in connection with Fig. 2. Likewise, the fluorescent plate 34 and filter 36, forming the lower set of light conversion and selection elements, convert the ultraviolet 253.7 mmu radiation passing through those elements into visible light, so that the response of the lower photocell 33 will be substantially entirely dependent upon the amount of 253.7 mmu radiation passing through the window 36.

The photocells 31 and 33 comprise part of an electrical control system for controlling a reversible motor 45. The control system for the motor 45 is indicated diagrammatically in Fig. 3 by the box 46. The details of this electrical control system will be fully described below. The electrical control system and the reversible motor 45 are energized from the source of alternating current as indicated by the circuit diagram in Fig. 3.

The reversible motor 45 operates the photometer by shifting the photometer member 3I back and forth in different positions across and in front of the upper opening 29. The driving connection between the motor-45 and the variable aperture member 3l is indicated in Fig. 3 by the broken line connection therebetween. Referring particularly to Fig. 4, this driving relationship between the motor 45 and the variable aperture member''! is shown in detail. A Worm 41 provided on the end of the rotor vshaft 48 of the reversible motor 65, serves to drive a worm wheel 49. A cord 56 runs over a pulley 5I on one side of the worm wheel 43 and a second pulley 52 mounted to the left of the photometer member 3I. One end of the cord 56 is fastened to the upper right hand corner of the photometer member 3I at 53, and the other end of the cord 56 is fastened to the upper left hand end of the photometer member 3l as indicated at 54. The pulley 52 is carried on a bell-crank lever 55 which is pivotally supported at the point 56. A spring 51 connected to the lower arm of the bell-crank 55 and a rigid part of the recorder, serves to tension the pulley 52 toward the left, thereby maintaining the cord 50 in a taut condition.

The record of the concentration recorder is made on a time-driven chart 58 by a stylus or pen 59 carried on the end of an arm 66 extending from the left hand side of the photometer member 3I.

In operation, the concentration recorderis first adjusted for zero reading. When used to .measure and record the concentration of ozone 4photometer member 3l has different positions ranging `from that, corresponding to zero ozone concentration to that corresponding to the maximum'` ozone concentration which the recorder is .adapted tomea'sure.v In making thezero adjustment the width of the window 30 is regulated by the shutter 32 so that the system will be balanced when the photometer member 3| is in zero position. That is, the Width of the lower window 30 is adjusted so that the amount of 253.7 mmu radiation passing therethrough is sufcient to effectively balance the amount of 253.7 mmu radiation passing through the photometer, when the member 3| is in its zero position. After this adjustment has been made, the recorder is in condition to measure and Arecord ozone concentration.

When the concentration recorder is'put into operation and ozone is circulated through the upper absorption cell 26, the intensity of 253.7 mmu radiation transmitted through this cell will be reduced in accordance with the concentration of ozone therein. As a result, the amount of 253.7 mmu radiation passing through the photometer will be correspondingly reduced, and with the photometer member 3| in its zero position, will not be sufficient to balance the amount of the same radiation passing through the lower window 30. Accordingly, the control system will be unbalanced, and the reversible motor will be operated so asA to shift the photometer member 3| from its zero position to a position where a sufiicient amount of the 253.7 mmu radiation is passed to balance that passing through the lower window 30. Thereafter, as the concentration of the ozone circulated through the absorption cell 26 changes from time to time, the photometer member 3| will be shifted from one position to another so as to keep the system in balance. The concentration will be recorded on the chart 58 by the element 59 which shifts with the photometer member 3|. The details of the photometer and the electrical control system are described below.

It will be seen that the photometer system, of the concentration recorder is of the so-called "null balance type. That is, a definite relationship is maintained between the amount of 253.7 mmu radiation passing through the photometer comprising the photometer member 3| and the opening 29, and the amount of the same wave-` length radiation passing through the adjustable lower window or aperture 3U. tage afforded by the employment of the null balance type of photometer system is that the' accuracy of the concentration recorder is not affected by changes in output of radiation from the vapor lamp 25 due to changes in line voltage. f

Photometer system For accuracy and convenience, it was found desirable to provide a photometer having a linear scale so designed that the amount of shift of the photometer member 3| from its zero position required to balance the system should be a linear or straight-line function of the ozone concentration in the absorption cell 26. Reference may be made to Figs; 5 and 6 of the drawings for a detailed description of the variable aperture member 3|. (Fig. 5 is a rear View of the photometer member 3| in respect to its position shown in Figs. 3 and 4 with the opening 29 indicated in broken outline.)

It will be noted that the variable .aperture member 3| has three similar elongated openings The great advan-` 6|, 62, and 63 of exponential shape formed therein. Three openings 6|, 62 and 63 are used soas to reduce photometric error. If -a single large opening were used instead, it will be seen, on referring to Fig. 3, that the points of fluorescence on the plate 33 would move from a central area to cover most of the plate 33 on shifting the member 3| from its zero position shown in Fig. `4-to its opposite position where the greatest amount of light is passed thereby. This fanning or wid@ ening out of the excited iiuorescent area might give rise to a photometric error, since ,the ref sponse of the upper photocell 31 to fluorescent light of given source intensity depends upon the position of the source on the fluorescent plate 33. Theoretically this error would be minimized to a negligible value if a large numberof equally spaced openings having parallel axes'were cutin the photometer member 3|. Since such an arrangement would be impractical, the three elongated openings 6|, 62and E3 were chosen. Ihe photometric error with the three openings has been found to be sufficiently small so thatv the over-all accuracy of the recorder is not impaired.

The calculation of the shape'of the openings 6|, 62 and 63, may be explained as follows, with reference to Fig. 6:

g=width of the opening 29,

w=total opening in member 3|,

Let =distance on recorder chart=distance oi' motion of the member 3| from the origin or zero position.

We know that the transmittance of the ozone is:

T=10*cf, where a=extinction coefficient=69,7[)0

cm.2/g.

t=thickness of ozone in cm.

c=concentration of ozone in g./cm.'`.

Since we desire a linear scale, c=lc2m- The photometric method calls for constant flux of 253.7 rnmu radiation going to the fluorescent plate; hence, calling :rm the maximum displacement .in operation of the photometer member 3|,-` we may Write Y where T'mn is the value of T at mm and at maximum recorded concentration. The object is to find a function of .r which will satisfy the above integral equation. It is easy to show that the solution is a simple exponential function:

Put f(:r)=AeB. Then, substituting and integrating, we obtain:

or (8) 80cm-m) =e2,303k2at(mmm) and,

B=2.13037c2at therefore,

for) =`A1ok2m when 1.1i Finally, the equation for the totalopening in the exponential opening becomes v With these values, Equation 9 becomes:

(10) f(:c) (2.20) .10-0.037/1089f)cm.

.Computations were made from Equation 10,`

andthe results are presented in the following table:

Table IV a: (cm.) j' (I) (cm.)

" The values given in Table IV are equally divided between the three parallel elongated openings B'I, 62 and 03. In the photometer member designed for the working embodiment of Vmy invention, the axes of the openings 6I,'62 and 63 are each separated by a distance of 0.85 cm. The openings 6h62 and 63 are somewhat longer than 3.5 inches (mm) so as to permitoverplay at zero and maximum concentrations. (A distance on the recording chart of exactly 3.5 inches was chosen for the range in ozone concentration of from 0.0 to 1.0 percent.) As indicated in-the foregoing theory, all calculations have been based on concentration ofozone expressed in grams per cubic centimeter. (g./cc.). Percentage composition, based on weight, is made relative to the density of dry air at 21 C., 75 cm. Hg atmospheric pressure.

In making the above calculations it has bee assumed that all of the rays of 253.7 mrnu radia- V tion passed through the absorption cell in a direction perpendicular to the quartz windows thereof. In any practical arrangement this condition cannot be completely met and, therefore, the incident rays are not perpendicular to the absorption cell but actually cover a range of angles from zero degrees to a certain maximum value dependent upon the size of the light source, the size of the absorption cell, etc. On the basis of sound theory the error due to this deviation from the ideal picture may be calculated. Such calculations have been made for the dimensions used in the ozone recorder instrument described4 hereinafter. They showed that the actual cell thick- 12 ness (inside width) should be 0.98 of the theoretical thickness. Thus, with a theoretical inside cell thickness t of 0.400 cm., the actual inside cell thickness should be 0.4 x 0.98 or 0.392 cm.=0.1543 inch Electrical control system The electrical control system employed in connection with the concentration recorder diagrammatically shown in Figs. 3 and 4 constitutes an important feature of the invention, and involves the use of a novel type of electrical bridge circuit for controlling gas-filled electric valves. The principles of my electrical control circuit are described below in connection with Figs. 7 through 12.

Referring particularly to Figs. 7, 8 and 9, the

following observation was made in experiments with a single blocking-layer photocell on the input of an oscilloscope. With the photocell 65 connected across the input of the oscilloscope 56, as shown, and exposed to an intense source of light showing a strong periodic variation in intensity, a voltage wave of insignificant amplitude was observed on the fluorescent screen 6l of the oscilloscope. However, when the unearthed terminal of the input was connected to a short antenna, as indicated by the broken line, to pick up the sixty-cycle wave, the wave form on the vfluorescent screen 61 changed very markedly as sketched in Figs. 8 and 9. In Fig. 8 the sixtycycle sine wave is shown which is obtained when the photocell 65 is in the dark. However, when the photocell 65 is exposed to low illumination of either steady or fluctuating intensity, the sine wave is materially changed in one half part of the cycle as shown in the sketch of Fig. 9. The broken line part of the sketch in Fig. 9 indicates the normal sine wave pattern. The explanation off thechange'in sine wave as shown in Fig. 9, is thatillumination decreases the shunt resistant across the input terminals of the oscilloscope Efduring one-half of the cycle. Although it was known that the internal resistance of a blocking-layer cell depended upon the intensity of light falling upon the photocell, it was surprising to find 'that the sensitivity of change of wave form to light was very much greater than the direct photoelectric eiect, where a rapidly uctuating source of light is involved, and one is interested only in the alternating current component. By way of explanation, it appears that the direct photoelectrio effect was impaired by the low impedance of the blocking-layer photocell.

It lWas found that the above observation of the. sensitivity of wave form to light of a blocking-layer photocell could be used to provide an electrical bridge circuit which was very sensitive to small relative changes in light flux from two light sources so as to produce large changes in wave form. Such a bridge circuit is shown diagrammatically in Fig. 10 of the drawings..

Referring to Fig. 10, it Will be seen that the electrical bridge circuit comprises four legs connected to provide two parallel branches. One pair of the legs or one branch comprises adjustable impedance devices indicated diagrammatically at 10 and ll, and the other pair of legs constitutes the other branch, each leg including a blocking-layer photocell indicated diagrammaticallyat 'l2 and 73. The-photocells 72 and 'i3 should be matched for sensitivity, internal resistance and capacitance. Each of the pairs of legs are connected in series circuit relation and the 'pairs of legs are then connected in parallel 13; to provide a circuit having two parallel branches, as shown. The conductors 14 and 15 serve to con neet the bridge with a source of alternating current indicated diagrammatically at 18. Adjustable impedance devices indicated diagrammatically at 69 and 11 may be connected in shunt relation with the photocells 12 and 13 respectively. lThe adjustable impedance devices 69 and 11 may each include an adjustable resistor and an adjustable capacitor connected together either in series or parallel circuitrelationship. The input of an electronic amplifier indicated diagrammatically at 18 may be connected across the common connections 19 and 80 between each of the pairs of legs, as shown. The output of the amplifier 18 is connected to the input of an oscilloscope indicated diagrammatically at 8|.

Many interesting effects were observed in connection with this electrical bridge arrangement. When an alternating current voltage, within a range to which the electrical bridge circuit was sensitive, was applied across the bridge from the source 16, and the bridge balanced through the manipulation of the impedance devices 10, 1| and 11, the bridge circuit became very sensitive to small relative changes in light flux gathered by one of the photocells. When the cells 12 and 13 are in darkness, the bridge circuit may be balanced so as to obtain the residual wave 82 sketched in Fig. 1l. This residual wave is indicated by the full line having loops of equal amplitude above and below the reference line. Theoretically, if the photocells 12 and 13 were identical and completely matched for sensitivity, internal resistance and capacitance, the residual wave 82 .would be a straight line. y

The change in wave obtained when one of the photocells receives an increment in light flux or illumination not accompanied by a similar increment received by the other photocell, is indicated by tlie Waves 83 and 84, the wave 83 being designated. with dots and dashes, whereas the wave 84 is designated with uniform dashes.

Referring to the sketch of Fig. l1 it will be seen from the waves 83 and 84 that peaks 360 electrical degrees apart, relative to the potential source16 connected across the parallel branches ofA the bridge circuit, increase, and alternate peaks (180 phase difference) decrease, when one of the photocells receives an increment in illumination and, vice versa, the alternate peaksv rise and the first-mentioned set of peaks decrease when the other photocell receives an increment in illumination. The wave 83 represents the wave obtained when one of the photocells 12 or 13 receives the greater illumination, While the wave 84 represents the wave obtained when the other photocell receives the greater illumination. It should be noted that peaks of the same potential are produced during each half cycle of the potential source 16 when the relative illuminations of the two photocells are at proper values. This is most unexpected, and as will hereinafter appear, most useful phenomena. When light flux to the two cells 12 and 13 is greatly increased, but balance (through only change in relative flux), the residual wave 82 shown in the sketch of Fig. l1 docs not change greatly in either amplitude or phase, the change in phase being very small; moreover, the phenomenon is not significantly altered when a strongly pulsating light source (l-tube G, E. Mazda fluorescent lamp) is used.

It was found that the value of the alternating current voltage impressed on the bridge circuit was an important factor. When this voltage was raised to a certain maximum value (two or three volts), depending upon the particular circuit involved, the circuit was no longer sensitive to changes in illumination on the photocells 12 and 13, and an essentially sinusoidal wave form was observed on the screen of the oscilloscope 8|. However, when the voltage was again reduced to a value t0 which the bridge became sensitive, the wave forms shown in connection with sketch of Fig. 11 were again obtained.

It is apparent that the wave form patterns shown in the sketches in Fig. l1 are well suited for direct control of electric valves of the gasiilled type (Thyratron or Grid-glow tubes). The grids or control elements of the Thyratrons should be operated together and the plates operated apart by 180 electrical degrees.

In Fig. l2 of the drawings one type of electrical control system for the concentration recorder of Fig 3 is shown, employing the electrical bridge circuit principles described above in connection with Fig. l0. Referring to Fig. 12, the blocking-layer photocells 31 and 38 (Fig. 3) are indicated diagrammatically at 85 and 86 in two legs of an electrical bridge circuit. The photocells 85 and 86 are connected in series circuit relation in one branch of the electrical bridge by a resistor 81, and the other branch of the electrical bridge comprises a resistor 88. The input terminals of an amplifier, indicated diagrammatically at 89, are connected between the electrical midpoints of the bridge circuit as indicated at 90 and 8|. Since the photocells 85 and 86 cannot ordinarily as a practical matter be perfectly matched for internal resistance or capacitance, an adjustable resistor 02 and a variable capacitor 83 are connected in shunt circuit relationship with one of the photocells 85 or 86.

The bridge circuit may be energized from a transformer, indicated generally at 94, having its primary winding 95 connected for energization from a 1l5-volt alternating current source, and having a secondary winding 98 of few turns. The secondary winding 98 is connected across the branches of` the bridge circuit through an adjustable resistor 91 whereby the voltage V impressed across the bridge may be regulated. The value or the voltage V is ordinarily adjusted to about 0.25 volt.

The resistor 91 is a low resistant potentiometer rheostat having a resistance of the order of 1000 to 2000 ohms, the exact value not being critical. The resistors 81 and 88 may be 100G-ohm potentiometer rheostats, and the resister 92 may be a 10,000-ohm rheostat. The exact values of the resistance 92 and the capacitance .93 depend upon the degree of difference in o impedances of the photocells 85 and 86. It will be understood that these details of the electrical bridge circuit are not critical and that certain other arrangements may be used.

As stated, the wave form pattern obtained with 85 the electrical bridge is well suited for direct control of gas-filled electric valves, of the type commercially available as Thyratrons (General Electric) or Grid-glow tubes (Westinghouse).

Accordingly, the output of the amplifier 89 is capacitively coupled to the control grids of two such electric valves |00 and |0|, as shown. The

grid bias is supplied and the firing points of the electric valves |00 and |0| adjusted, by voltage from a battery indicated diagrammatically at. |02 through suitable adjustable resistance,

as'shown. Only low amplication 4is necessary,` and the amplier 39 may be of the conventional two-stage type.

The tube y| 03 is connected in series with one of the eld coils (not shown) of a reversible motor E33 while the other tube Iii `is connected in series with the other neld coil oi' the reversible motor. The laments or heater elements of the electric valves ||l|3 and Ii are connected for energization to the secondary winding |06 of a transformer |37, having its primary winding |08 connected across a 115-volt alternating current source. The motor |33 may be of the direct current, fractional horse power type and has one terminal of one' of its field-coils connected to one side ci the secondary winding I G4 of a transformer indicated generally at |35, While one terminal of the other eld coil is connected to the oppositeV side of the secondary winding |04. Each of the other terminals of the eld coils is connected through one of the tubes or EI and through the armature of the motor |33 to the center tap of the secondary Winding I4.

-It will be seen that the control grids of the electrontubes lil'and IBI are operated together while the plates thereof are operated 180 electrical degrees apart. As described in connection with Figs. 10 and l1, small changes in light uX to, for illumination of,` either of the blockinglayer photocells 85 and 85 will distort the residual-balance `wave of the bridge circuit so as to produce either the wave form 83 or 84 (Fig. 11), depending upon` which of-the photocells receives the greater illumination. Accordingly, when the balance between the illumination of the photocellsl 85 and 83 is changed in one direction 'one of the 'tubes' I8 or IIlI will re, while if the illumination is 4unbalanced in the opposite direction, the other tube will fire. Since each of the eld coils of -thevreversible motor |33 is connected with one of the electric valves IUS or Il, the motor will run in one direction or the other depending upon which of the tubes is caused to iire. Referring back to the operation of the concentration recorder as shown diagrammatically in Figs. 3 and 4, it will be seen that the bridge circuit will continue to be unbalanced and one of the tubes IBI) orV IGI will `fire until the motor I|l3 has driven the photometer member to a point where the bridge circuit is again balanced.

' Employing the principles of my invention described above, an ozone concentration recorder adapted to measure the concentration of ozone in air up to 1.0 per cent was constructed. The'details of this recorder are described below in connection with the remaining gures of the drawings.

Design of ozone recorder Referring to Figs. 13a, 13b, 14a and 14h, the recording instrument is housed in a box the frame elements of which comprise angle iron members |||i welded together at the eight corners of the box. The box is 29 inches long, 10 inches wide, from front to back, and 13 inches high. Three vertical partitions H2 and IIS, and one horizontal partition I I4 divide the interior of the box into four compartments. The four compartments may be designated as light source compartment H5, photocell compartment I I6, recorder compartment IIl, and rectier compartment I8. It will be noted that the rectifier compartment I I8 is4 that .portion of the instrument which is under the''partition ||4 and back of theV partition I|3. The recorder compartment includes that portion in front of the partition I I3 and extends over the rectier compartment II 8. The side walls (not shown) Vof the instrument may be constructed with lightweight sheet steel,

bent at the corners and bolted to the steel frame. The back wall should be hinged so that free accessrtothe recorder and rectifier compartments II1v and I|8 may be had. The front wall should contain an opening so as to permit ready access to the recording chart. Y

Referring to Figs. 13a, 14a, and 16 of the drawings, it will be seen that the vertical partition I II has a pair of beveled-edged upper and lower openings or apertures |23 and |2I', respectively, formed therein. A variable aperture, photometer member |22, constructed according to the theory described above in connection with Figs. 5 and 6, is shiftably supported on the right hand side (referring to Fig. 16) of the upper opening |26. The photometer member |22 is supported by a pair of upper and lower anged rollers |23, and an arm |24 fastened to the right hand end thereof which passes through a hole in the vertical partition |I2. The arm |24 is supported and guided between a pair of guide rollers |25 (Figs. 13b and 14h) mounted on the side of the partitionl I2.

A quartz-window ozone absorption cell I 26 is mounted in front of the photometer member |22. The absorption cell |26 is supported by a pair of conduits |21 which also serve to conduct ozonated air to and from the absorption cell |26 for circulation therethrough. A dummy, quartz-Window absorption cell |28 (Fig. 16) is supported in front of the lower window |2| by a pair of support members |29. Since the recorder is intended to measure the concentrations of ozone in air, it is not necessary to circulate air through the dummy absorption cell I 28. However, if the concentration' of a solute in a solvent were being measured, conduits would be connected with the dummy absorption cell |28 so as to circulate the clear solvent therethrough.

The rectangular separator |33 for the absorption cell |26 may be cut out of a brass plate and the two faces thereof ground so as to be parallel and as smooth as possible. The reduced diameter. nipples |34 entering the top of the frame |33, may be soldered into the couplings |35 and the separator |33. No organic material should be present in the conduits |2'I or the absorption cell |26 since such material will cause a rapid absorption of ozone and lead to an error in reading. The quartz-windows |38 may -be rmly held in place to the opposite sides of the separator |33 by pinch clamps (not shown), and the cell may be sealed by molten paraiin painted around the edges thereof and allowed to solidify. The lower absorption cell |28 may be constructed in the same manner as the absorption cell |26.

In order to adjust the Width of the lower window |2| so as to adjust the recorder for zero readings, a shiftable shutter |40 is provided having a supporting arm I4I (Fig. 14a) extending therefrom. The arm |4| is supported betweena pair of capped-pins |42 and the position of the shutter |40 may be adjusted by a screw |43 projecting into the internally threaded end of the arm |4|. The head of the screw |43 extends through the partition ||2 so that it may be reached with a screw driver and the position of the shutter |40 adjusted vby turningthe same..v A spring I 44 compressed between the partition I I2 and a. collar 45 17 on the end of the arm I4I serves to securely bias and hold the shutter |40 in position.

As shown in Figs. 13a, 15 and 16, an M-shaped mercury vapor lamp |50 may be used as a source of 253.7 mmu radiation. The lamp |50 may be of the type commercially available on the market as the Westinghouse Vterilamp. The characteristics or the radiation of such a lamp have been described above in connection `with the system of Fig. 2 of the drawings. The lamp |50 is supported on a backing member by a pair of bands |52 (Fig. 15) which are spring tensionecl by a pair of tension springs |53 inserted between the back |5| and retaining washers |54, as shown in Fig. 13s. ported from the bottom plate of the instrument box by a pair of uprights |55 fastened at their lower ends in a pair of blocks |56. The front face of the backing plate I 5I, which may be made of Bakelite, is smoked with magnesium oxide as indicated at |51 so as to substantially increase the amount of 253.7 mmu radiation radiated to the photometer part of the instrument. An opaque metal screen |58 (Figs. l5 and 16) is placed around the lamp I y5I) so as to block out all ultraviolet rays originating in the light source excepting those which proceed to the photometer assembly. The purpose of the screen |58 is to prevent unnecessary deterioration of wire coverings and other organic material in the light source compartment I 5.

Referring again to Figs. 13a, 14a, and 16 of the drawings, it will be seen that the light conversion and photocell system is mounted as a unit on the partition I I on the opposite side thereof from the photometer member |22 and the absorption cells 26 and |28. The unit is enclosed in an outside band |60 tting over four square posts ISI which project from the partition ||I. The front of the box is closed by a plate |62 having openings to accommodate a pair of upper and lower photocells I 63 and |54, respectively. The photocells I 63 and |65 are held in place in the plate |62 by the ilanges |65 and |66 thereof which engage the plate |62, and two sets of clips |61 (Fig. 13e). The photocells |63 and |64 are of the blocking-layer, iron-selenium type. A pair of terminals I 6B and I 69 project from the rear of each of the photocells |63 and |64, respectively.

Each of the photocells |63 and |64 is covered with a red lter |10. The absorption properties of the filters correspond to those of the red lters I8 described in connection with Fig. 2 of the drawings. As stated, these ilters may be of the type known as Wratten No. 25.

A pair of fluorescent glass plates |'|I and |12 are mounted in front of each of the photocells |63 and |64, respectively, and supported in the thin metal frame |13. The fluorescent plates I1I and |12 are coated with a lm or deposit of cadmium borate phosphor and have the excitation characteristics describe-d in connection with the fluorescent plate |1 of Fig. 2 of the drawings. Horizontal separators |14 and |15 (Fig. I6) are provided in the unit to prevent fluorescent light from either of the fluorescent plates |1| and |12 from reaching the photocell |63 or |64 associated with the other nuorescent plate. The interior surfaces of the enclosing members |60 and |62 and the surfaces of the frame |13 and separators |14 and |15 should be painted in at black so as to minimize the effects of stray light.

From Fig. 16, it will be noted that the position The backing member |5| is suplil of the mercury vapor lamp |50 is so adjusted that the center thereof is at approximately the same elevation as the center of the upper absorption cell |26 and the photometer, whereas the dummy absorption cell |28 is arranged at some distance (approximately 2 inches) below the line of centers of the lamp |50 and the photometer. This arrangement is made so as to obtain good photometric accuracy since the radiation should pass through the absorption cell |26 and photometer in as nearly parallel rays as possible.

On the other hand, it is not a matter of importance if the radiation from the lamp |50 strikes the lower iluorescent plate |12 at an oblique angle after passing through the dummy absorption cell |28, and the lower Window |2|. This is due to the fact that it is only necessary that the percentage change in light flux passing through the Window |2| and incident upon the lower uorescent plate |12 due to change in output from the lamp |50, be the same as for the corresponding percentage change in flux passing through the absorption cell |26, the photometer, and incident upon the upper uorescent plate |'I I.

There has been found to be an optimum separation between the upper fluorescent plate I1I and the photometer member |22. This optimum separation eliminates error and the necessity for a perfect uniformity of the coating of cadmium borate phosphor on the plate. This will be understood on reference to Fig. 16 where it will be seen that there is a Wide divergence or spread of the rays passing through any one of the three narrow elongated openings in the photometer member |22. Thus, the diagrammatic rays fan out in passing through the photometer member |22, so as to cover approximately one-half of the area ofthe fluorescent screen or plate |1I. This wide distribution and overlapping of the rays serves to reduce error due to variation in thickness of the film of cadmium borate phosphor.

The reversible motor for shifting the photometer member |22 in opposite directions, is shown in Figs. 13a and 14h mounted upon a platform |8| supported by posts |82 extending upwardly from the bottom of the instrument box. The armature shaft |83 extends from the left hand side of the motor |80 and carries a worm |84 which engages and drives a worm wheel |85. The worm wheel |85 is mounted on a horizontal shaft |86 supported at one end in a bearing |81 and at the other end in a bearing in the vertical partition I. A pulley |90 is secured to the shaft |86 adjacent the vertical partition I I over which a driving cord I9I runs. One end of the cord |9| is secured to the upper left hand corner of the photometer member |22 as indicated at |92, While the other end of the cord is secured to the upper right hand corner of the photometer member |22 as indicated at |93. The driving cord ISI passes from |92 around the pulley |90 and thence around an idling pulley |94 carried on a pin projecting from the upper end of an L-shaped lever |95. The pin on which the pulley |94 is supported passes through a window |96 cut through the Vertical partition I||, and the lever is pivotally supported to the partition III at |01. A spring |98 serves to bias the idling pulley |94 toward the right and keep the cord |9| under a tension substantially greater than that required to move the photometer plate |22 and the recording pen or stylus 200 (Fig. 13b). In this manner, friction is minimized and dimensional changes in the length of the driving cord I 9| are automatically compensated for.

annoia 'Referringto Figs. 13s and'l, for a'l descrip,- tion of the recordingapparatus, it will be seen that a synchronous Amotor 28! is mounted .on top of the rectifier compartment i l2; A small pinion gear 202 (Fig. 14h) is carried on the driveshaft of the motor 22| and meshes with alarge gear wheel 203 mounted on one end of a shaft 222; The lefthandend of the shaft 222 is journaled in a bracket 225 which also supports the synchronous motor 2G I, and the right hand end is journaled in a b1ock'265 carried on a bracket 22?. The shaft 204 also carries a worm 268 which serves to drive a worm Wheel 2m keyed to the reduced end 2II (Fig. 13b), of a stub shaft 212. The stub shaft 2 I 2 is journaled in a bearing 2 I 3 carried on top of the bracket 120'!V as shown.

A collar member 2id' having a large diameter flange 255 is carried on the front end of the shaft 2l2. The flange 2i5 serves as a back support to which a chart disc 2 l5 is held. The chartv disc ZIBv ts over the end of the shaft 2I2 and may be secured to the flange 2 I5 by screws passing therethrough. Chart paper may be held against the chart disc 2l?) by a large nut 2i?. A thin metal plate 22) having allarga circular opening therein to accommodate the chart disc 2I6 is vertically supported around the disc 2lb. Ears or tabs 22I are bent out from the thin sheet 222 at diierent positions therearoundand serve to retain alchart paper 222. in vertical position on the disc ZIS.

The synchronous motor 20! drives the chart disc 2I6 at avconstant` speed and a record of ozone concentration is made thereon by the stylus 223 of the recording pen 222. The stylus 223 is carried in a receiver 22:2 having a removable cap 225. A weak spring 226 within the receiver 22d serves to pressk the stylus 223 gently against the chart paper on the chart disc 216. The recording pen 22iisv adjustably mounted on the end of the square arm'22lby a pin 221. The pin 22'! is adjustablewithin a socket in the end of the arrn 222 and may be fastened.v imposition by a set'screw 223..

In order that the ozone vconcentration may be conveniently read at any time, a scale 22Sv (Fig. 14s) is supported. beneath the. arm 24, and a pointer d@ is vcarried below the arm |24 so as to passover the divisions ofthe scale 22S. The scale229 is calibrated-in percentage ozone concentration from 0.0 to 1.0 per cent, as shown.

rihe electrical system'flrst used in my ozone concentration recorder is shown in-Fig. 17 of the drawings, to which `reference may be had for a description thereof. The recording instrument may be energized from 115-volt alternating current source, as indicated. The synchronous motor 2I which drives the chart disc 2I6 of the recorder' is connected for energization with the 115'volt line through aA toggle switch 230 so that itmay be controlled independently of the other elements in the apparatus.V The mercury Vapor lamp i553 is connected across the secondary 23! of a step-up transformer 232. The primary 233 of this transformer is connected across the 115- volt line through a toggle switch 232, as shown.

The blocking-layer photocells I and I (Fig. 16) are connected in one branch of an electrical bridge circuit corresponding substantially to the electrical bridge described in connection with 12. One branch of the bridge comprises the two photocells ISS and Ilinterconnected in series circuit relation by a resistor 235, andthe other branchcomprises a potentiometer typerheostat 225i.l The two branchesofthe bridgef- Cil are' connected in parallel across the terminalsof the secondary winding 231 of a step-down transformer 238. The'primary windingV 2391s' connected for energization across the 1l5volt line, as shown. The transformer 232 is approximately the size andcapacity of a small door-bell ringe ing transformer, and a secondary 231 consists' of only a few turns so that the voltage V impressed across the bridge circuit will be in the order of 0.25 volt. Since the photocells M53 and itil cannot ordinarily be perfectly matched for impedance, an adjustable resistor 2d@ and a variable capacitor 2li! are connected in shunt circuit relation with at least one of the photocells so as to balance them for difference in internal resistance and capacitance. The photocells E63 and Milt may be thus balanced for internal resistance and capacitance by proper adjustment of the resistor 22d and capacitor 2M.

The input of an electronic amplifier, indicated diagrammatically at 2fi5, is connected across the electrical mid-points of the bridge circuit, as ina. dicated. The amplier 225 may be energized from the ll-voit current source through a pair of conductors or leads 2F56 and '222. The output of the ampliner 2i5`is'capacitively coupled to the control elements or grids 2&2 and 229 of a pair of gas-lled electric valves 252 and 25|.l The tubes 252 and 251 are of the four-element type and are presently classified as FG-QS (General Electric). The grid bias of the control elements 228 and 229 may be adjusted from a B battery indicated diagrammatically at 252,v through suitable adjustable resistance. The heated filaments 252 and 25? of the electric valves are connected for energization with the secondary 252 of a transformer. indicated generally at 259.

One of the field coils 222 of the reversible motor i8@ is connected in'series circuit relation with the electric-valve 252, while the other eld coil 255i is connected in series circuit relation with the other electric valve 25i. As will be seen, the circuit for the i'leld coil 2S@ is completed through one-half of the secondary winding 262 of the transformer 25%, the armature of the motor |83, and the tube 25), the armature being connected to the center-tap of the secondary winding 262. rilhe circuit for the field 'coil 265 is completed through the other half of the secondary 222;V the armature of the motor and the other tube 25E. The primary winding. 253. of the transformer 229 is connected for venergization across the 11E-volt source, as shown. A toggle switch 222 is provided in the 1l5volt linewhich serves to control the energizationofthe recordingin'-l strument except for the Sterilamp lamp lei! and the synchronous recorder motor 2S! i The fourth elements 265and-2f ofthe tubes 252 and 25E serveto give stea'dier operationV of the electrical system. It willbe seen that the ground output terminal of the amplifier 265, the fourth tube elements Zitand '266, and the center taps of the secondary transformer windingsv 258 and 222 are interconnected or grounded.

In operation of my ozone concentrationV recorder, the electrical ycircuit control system is rst adjusted, conveniently with the help cf an oscilloscope. With the mercury-vapor lamp I5@ turned off, the electrical bridge circuit including the photocells H53 and Il is balanced so as to obtain a balanced residual waveform as described in connection with Figs. l0 andllof the drawings. Then, the mercury vapor lamp I tjis turned on and with the absorption cell |25 -entirelyffree of ozone, the width of the lower window I 2| is adjusted with the shutter |49 so that the system including the reversible motor |38 is balanced When the photometer member |22 is in its zero position. As a check (probably necessary only in the original test oi the instrument) the intensity or output of radiation from the vapor lamp :|59 is varied through wide limits so as to ascertain that the recorder gives a constant reading in spite of these variations.

`After the recorder has been thus initially adjusted, the ozone-air mixture is circulated through the absorption cell |25 by suitable pumping apparatus. As 253.7 mmu radiation is absorbed by the ozone on passing through the cell |26, the system becomes unbalanced and one of the tubes 250 or 25| will nre over a longer portion of the cycle than the other. Accordingly, the reversible motor |80 will rotate in such a direction as to shift the photometer member |22 to a position permitting more 253.7 mmu radiation to pass and thereby vbring the vsystem back into balance. Conversely, in the event that the concentration of ozone in the absorption cell |28 decreases, thereby ypermitting an increased amount of 253.7 mmu radiation to pass, the firing period oi the tubes 250 and 25| will again become unbalanced, but 4in'an opposite direction, so as to rotate the motor |50 in an opposite direction. In turn, the photomete'r member |22.will be shifted so as to decrease the amount of radiation passing through the' photometer. and bring the system b-ack in balance. i

' As described, the'motion of the variable aperture, photom'eter member |22 in 'following the concentration of ozone in the absorption cell |28 is translated to the recording pen 20D. In this mannen'the pen makes a record of the ozone concentration on the chart paper 222 (Fig. 14e). 'f Although my ozone concentration recorder, as described above, operated satisfactorily in a practical manner, it was found that even much more satisfactory operation of the recorder could be obtained by modifying the electrical bridge of the electrical control system of Fig. 17. This modifi-l cation consisted in substituting light-sensitive tubes or photocells of the photo-emissive type (vacuum or gas-iilled phototubes) for the photocells |63and |64 (Fig. 17) which, as stated, were of the blocking-layer type.

The modied bridge circuit is shown diagrammatically in Fig. 18 of the drawings as electrically interconnected between a transformer 210 and the ampliiier 245 (Fig. 17). The transformer 210 corresponds in function to the transformer 238 (Fig. 17), but the transformer ratio thereof is greater than that of the transformer 238 so as to impress a greater voltage across the bridge circuit. Whereas it was found that the bridge circuit of Fig. 17 had its greater sensitivity when a voltage in the order of 0.250 was impressed across it, it has been found that the bridge circuit of Fig. 18 should have an impressed voltage in the order of 3 to 5 volts.

One branch of the modified bridge circuit of Fig. 18 is provided with a potentiometer type rheostat 273 while the other branch of the bridge is comprised of two phototubes 214 and 275 of the photo-emissive type interconnected in series circuit relation. A small variable capacitor 271 isconnected in shunt relationship with each of the phototubes 214 and 275, as shown, so that any slight difference in capacitance of the two tubes may be corrected. The input of the electronic amplifier 245 is connected across the elec-v trical mid-point of the bridge circuit, as indid cated. Except for the modification of the electrical bridge as described, the electrical control system by which the Thyratrons or gas-filled valves 255 and 25| are controlled is the same as the control system shown in Fig. 17.

The residual Wave obtained with the bridge of Fig. 18 is very similar to that observed when blocking-layer photocells are employed (Fig. l1), although the dependence of the amplitude of the residual Wave on light level is much stronger. When the phototubes 27d and 275 are in total darkness, the residual Wave may be made zero;

then, when the light level on the tubes is brought up and balanced, the residual Wave comes into existence, and increases with increasing light level.

The use of phototubes of the photo-emissive type as described in connection with Fig. 18, has led to much more satisfactory operation of the recorder, since sensitivity is appreciably greater and the stability or freedom from drift has been greatly increased. Furthermore, it is easier to obtain photctubes of the photo-emissive type which are matched because it is only necessary that these tubes be similar in the current-voltage characteristic, Whereas photocells of the blocking-layer type must match in current-voltage characteristic, internal resistance and capacitance.

As another modification of the electrical bridge of the invention, the photocells employed therein may be a pair of the early type selenium cells. This type of cell is of the photo-conductive type and involves ordinary conduction through a thin lm of selenium, which exhibits a change in resistance when illuminated.

Although I have described an embodiment of my invention specically adapted to measure and record concentrations of ozone in air, it will be understood that modications and adjustments may be made so that by applying the same principles of invention, instruments may be made for measuring and recording concentrations of other gases and vapors, as Well as certain solutes in solvents.

It will be understood that in apparatus of this nature, involving as it does a relatively largeA number of parts and elements organized into different systems, certain changes, modications and other arrangements may be made without departing from the principles and scope of the invention. Accordingly, all matter described above or shown in the accompanying drawings is intended to be interpreted as illustrative and not in a limited sense.

I claim:

l. Means adapted to control the operation of electrical apparatus in response to small changes in light iiux from a light source, comprising a, gas lled valve having control and plate elements, an electrical bridge circuit having four legs, one pair of said legs each including an impedance device and the other pair each including 9, polarized photocell, one of the photocells being adapted to receive light iiux from said light source, the legs of each pair being connected together in series circuit relation, said polarized photocells being connected with unlike electrodes connected together, and said pairs of legs being connected in parallel circuit relation, a low voltage source of alternating current connected across the parallel connected pairs or legs, a high voltage source of alternating current which is of the same frequency as, and which is in phase with, said low 

